Journal of Physical Organic Chemistry最新文献_第8页

Substitution effect on the adiabatic ionization potential, vertical ionization potential, electrophilicity, and nucleophilicity of some hydantoin drug derivatives: Computational study 乙内酰脲类药物衍生物的绝热电离势、垂直电离势、亲电性和亲核性的取代效应：计算研究

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-09-11 DOI: 10.1002/poc.4565

Zaki Safi, Nuha Wazzan

{"title":"Substitution effect on the adiabatic ionization potential, vertical ionization potential, electrophilicity, and nucleophilicity of some hydantoin drug derivatives: Computational study","authors":"Zaki Safi, Nuha Wazzan","doi":"10.1002/poc.4565","DOIUrl":"https://doi.org/10.1002/poc.4565","url":null,"abstract":"In the current paper, the adiabatic ionization potentials (AIP) for 29 hydantoin derivatives and hydantoin-based drugs such as allantoin, phenytoin, mephenytoin, nilutamide, iprodione, nitrofurantoin, and ethotoin were calculated using the double hybrid ωB97XD density functional theory (DFT) in coupling with 6-311+G(2df,2p) basis set at the B3LYP/6-31+G(d,p) optimized geometry. The neutral and cationic radicals of the examined species were firstly optimized using the B3LYP/6-31+G(d,p) level. Final energies were improved by single point calculation using 16 different DFT methods such as B3LYP, ωB97, B97D, TPSSTPSS, M06-2X, …, and so forth, with 6-311+G(2df,2p) basis. Statistical tools such as root mean square error (RMSE) was used to examine the accuracy of the DFT method with respect to the standard reference AIP values. These standard references were calculated, for 12 hydantoin derivatives with less than nine non-hydrogen atoms, by taking the average values of the AIP computed using the G4, G3B3, and CBS-QBS methods. The vertical ionization potentials (VIPs), the vertical electron affinity (VEA), and global quantum parameters such as electrophilicity and nucleophilicity of the 29 molecules were also calculated. Substitution effect on the AIP, VIP, VEA, fundamental gap, electrophilicity, and nucleophilicity of the species under probe was studied and discussed. The results reveal that substitution of electron withdrawing group (EWG) raises the AIP and VIP, electrophilicity, and the fundamental gap, while substitution of electron donating group (EDG) raises the VEA and the nucleophilicity. Furthermore, the condensed Fukui functions were used to identify the active centers for nucleophilic, electrophilic, and free radical attacks.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50129563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dichlorocarbene: From Jack Hine to Robert Moss 二氯苯:从杰克·海因到罗伯特·莫斯

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-08-09 DOI: 10.1002/poc.4563

Matthew S. Platz

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Research on the Reaction Mechanism of 2,4,6‐Trinitrotoluene Resource Utilization I:Formation of 2,4,6‐Trinitrobenzoic Acid in Acetic Acid with N,N',N″‐Trihydroxyisocyanuric Acid (THICA) Catalyst 2,4,6‐三硝基甲苯资源利用反应机理研究ⅰ:N,N'，N″‐三羟基异氰尿酸(THICA)催化剂在乙酸中生成2,4,6‐三硝基苯甲酸

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-08-03 DOI: 10.1002/poc.4564

Guan Zhang, Jin Li, Zongkuan Liu

{"title":"Research on the Reaction Mechanism of 2,4,6‐Trinitrotoluene Resource Utilization I:Formation of 2,4,6‐Trinitrobenzoic Acid in Acetic Acid with N,N',N″‐Trihydroxyisocyanuric Acid (THICA) Catalyst","authors":"Guan Zhang, Jin Li, Zongkuan Liu","doi":"10.1002/poc.4564","DOIUrl":"https://doi.org/10.1002/poc.4564","url":null,"abstract":"As an organic molecule catalyst, N,N',N\"‐trihydroxyisocyanuric acid can selectively catalyze the oxidation of the methyl group of waste 2,4,6‐trinitrotoluene to generate 2,4,6‐trinitrobenzoic acid. This reaction can avoid environmental pollution by inorganic heavy metal catalysts. In this study, four reaction stages of this catalytic reaction were designed and validated computationally at the M06‐2X‐D3ZERO/6‐311G(d,p) level using the acetic acid solvent model. These validations include transition state searches, intrinsic reaction coordinate calculations, reactant and product optimizations, and frequency calculations. The final reaction network of 23 transition states shows that after N,N',N\"‐trihydroxyisocyanuric acid activation and common reaction, the network bifurcates into two stages: alcohol to carboxylic acid and aldehyde to carboxylic acid. Although the former stage releases about 155 kcal/mol of Gibbs free energy, less than the 177 kcal/mol from the latter stage, the overall reaction equation shows that the pathway including former stage does not consume the catalytically active substance IM_T2, which saves the energy required for reactivation and is thus more favorable. Furthermore, the key transition states in the reaction network include bimolecular substitution reactions and proton hopping transfer reactions. Analyses of their interaction region indicators and intrinsic reaction coordinate results demonstrate strong selectivity. Additionally, the energy barriers and heat releases of the latter are twice and 1.3 times greater than those of the former, respectively. In summary, this study elucidated two competitive reaction pathways and identified the more energetically favorable and selective pathway, it provides useful insights for further optimization of industrial utilization of 2,4,6‐trinitrotoluene.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45453912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Research on the reaction mechanism of 2,4,6-trinitrotoluene resource utilization I: Formation of 2,4,6-trinitrobenzoic acid in acetic acid with N,N′,N″-trihydroxyisocyanuric acid catalyst 2,4,6-三硝基甲苯资源化反应机理研究Ⅰ：N，N′，N〃-三羟基异氰尿酸催化剂在乙酸中生成2,4,6-三甲硝基苯甲酸

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-08-03 DOI: 10.1002/poc.4564

Guan Zhang, Jin Li, Zongkuan Liu

{"title":"Research on the reaction mechanism of 2,4,6-trinitrotoluene resource utilization I: Formation of 2,4,6-trinitrobenzoic acid in acetic acid with N,N′,N″-trihydroxyisocyanuric acid catalyst","authors":"Guan Zhang, Jin Li, Zongkuan Liu","doi":"10.1002/poc.4564","DOIUrl":"https://doi.org/10.1002/poc.4564","url":null,"abstract":"As an organic molecule catalyst, N,N′,N″-trihydroxyisocyanuric acid can selectively catalyze the oxidation of the methyl group of waste 2,4,6-trinitrotoluene to generate 2,4,6-trinitrobenzoic acid. This reaction can avoid environmental pollution by inorganic heavy metal catalysts. In this study, four reaction stages of this catalytic reaction were designed and validated computationally at the M06-2X-D3ZERO/6-311G(d,p) level using the acetic acid solvent model. These validations include transition state searches, intrinsic reaction coordinate calculations, reactant and product optimizations, and frequency calculations. The final reaction network of 23 transition states shows that after N,N′,N″-trihydroxyisocyanuric acid activation and common reaction, the network bifurcates into two stages: alcohol to carboxylic acid and aldehyde to carboxylic acid. Although the former stage releases about 155 kcal/mol of Gibbs free energy, less than the 177 kcal/mol from the latter stage, the overall reaction equation shows that the pathway including former stage does not consume the catalytically active substance IM_T2, which saves the energy required for reactivation and is thus more favorable. Furthermore, the key transition states in the reaction network include bimolecular substitution reactions and proton-hopping transfer reactions. Analyses of their interaction region indicators and intrinsic reaction coordinate results demonstrate strong selectivity. Additionally, the energy barriers and heat releases of the latter are twice and 1.3 times greater than those of the former, respectively. In summary, this study elucidated two competitive reaction pathways and identified the more energetically favorable and selective pathway, and it provides useful insights for further optimization of industrial utilization of 2,4,6-trinitrotoluene.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50118926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Machine learning-assisted study of correlation between post-transition-state bifurcation and initial phase information at the ambimodal transition state 机器学习辅助研究了过渡态后分岔与双峰过渡态初始相位信息之间的相关性

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-08-01 DOI: 10.1002/poc.4561

Tatsuhiro Murakami, Yuya Kikuma, Shunichi Ibuki, Naoki Matsumoto, Kanon Ogino, Yu Hashimoto, Toshiyuki Takayanagi

{"title":"Machine learning-assisted study of correlation between post-transition-state bifurcation and initial phase information at the ambimodal transition state","authors":"Tatsuhiro Murakami, Yuya Kikuma, Shunichi Ibuki, Naoki Matsumoto, Kanon Ogino, Yu Hashimoto, Toshiyuki Takayanagi","doi":"10.1002/poc.4561","DOIUrl":"10.1002/poc.4561","url":null,"abstract":"The Diels–Alder cycloaddition of cyclopentadiene and nitroethene, the intramolecular cycloaddition between a diene and triene, and the Diels–Alder cycloaddition of 2-hydroxyacrolein with 1,3-butadiene involving post-transition-state bifurcation (PTSB) were studied. These cycloaddition reactions were investigated using quasi-classical trajectory (QCT), classical molecular dynamics (MD), ring-polymer molecular dynamics (RPMD) simulations, and supervised machine-learning binary classification techniques. Room-temperature dynamics simulations started from the ambimodal transition state (TS) using the QCT, classical MD, and RPMD methods presented similar dynamics. Binary classification revealed that the initial geometry displacement from the ambimodal TS for the Diels–Alder cycloaddition of cyclopentadiene and nitroethene contributed to the branching dynamics and that the initial momenta for the intramolecular cycloaddition between a diene and triene and the Diels–Alder cycloaddition of 2-hydroxyacrolein with 1,3-butadiene played a significant role in the bifurcation dynamics.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4561","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46305728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Charge localization in bis(dioxaborine) radical anions 双(二恶aborine)自由基阴离子的电荷定位

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-08-01 DOI: 10.1002/poc.4562

Álvaro Moneo, M. Fernanda N. N. Carvalho, João P. Telo

{"title":"Charge localization in bis(dioxaborine) radical anions","authors":"Álvaro Moneo, M. Fernanda N. N. Carvalho, João P. Telo","doi":"10.1002/poc.4562","DOIUrl":"10.1002/poc.4562","url":null,"abstract":"The mixed valence (MV) radical anions of several bis(dioxaborines) with aromatic bridges of different length were studied by Vis/NIR spectroscopy, cyclic voltammetry, and theoretical calculations. The phenyl-bridged (1), the biphenyl-bridged (2), and bithiophene-bridged (5) radical anions show intense low-energy intervalence bands with vibrational structure typical of charge delocalized mixed valence species in the range of solvents studied. However, by subtracting from the experimental spectra of 2− in MeCN the fraction corresponding to the delocalized part (taken as the spectrum in tetrahydrofuran [THF]), we get a localized charge-transfer bands that show a significant cutoff effect at the low-energy side, as predicted by classical Marcus–Hush theory. In the radical anions with three aromatic rings on the bridge, the localization of the charge changes with solvent. These radicals are predominantly charge-localized in the high λS solvent MeCN, charge-delocalized in the low λS solvent THF, and show both type of intervalence bands in DMF. Experimental results and theoretical calculations show that the electronic coupling between dioxaborine units in these three-ring bridged radical anions increases with the number of thiophene rings on the bridge.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45727250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Study of the chlorogenic acid extraction with choline chloride‐based deep eutectic solvents and its DFT non‐covalent interactions analysis 氯化胆碱深共晶溶剂萃取绿原酸的研究及其DFT非共价相互作用分析

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-07-21 DOI: 10.1002/poc.4560

Ilse V. Herrera‐Beltrán, Mauricio Méndez‐Torruco, M. Matus, Z. Domínguez

引用次数: 0

Study of the chlorogenic acid extraction with choline chloride-based deep eutectic solvents and its non-covalent interactions analysis 氯化胆碱基深共晶溶剂萃取绿原酸的研究及其非共价相互作用分析

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-07-21 DOI: 10.1002/poc.4560

Ilse V. Herrera-Beltrán, Mauricio Méndez-Torruco, Myrna H. Matus, Zaira Domínguez

{"title":"Study of the chlorogenic acid extraction with choline chloride-based deep eutectic solvents and its non-covalent interactions analysis","authors":"Ilse V. Herrera-Beltrán, Mauricio Méndez-Torruco, Myrna H. Matus, Zaira Domínguez","doi":"10.1002/poc.4560","DOIUrl":"https://doi.org/10.1002/poc.4560","url":null,"abstract":"The microwave-assisted extraction of the main phenolic component of green coffee beans, chlorogenic acid (CGA), was carried out employing deep eutectic solvents based on choline chloride and five different hydrogen bond donors (HBD) in a 1:2 ratio. The best performance for the extraction process of CGA was reached by the mixtures of choline chloride/ethylene glycol and choline chloride/urea. To understand the various interactions between the phenolic compound and the two most efficient deep eutectic solvents, computational calculations were carried out at the density functional theory (DFT) level, as well as Atoms in Molecules (AIM) and Non-Covalent Interactions (NCIs) analyses. In that way, a variety of hydrogen bond types were found in every structure. Nevertheless, the CGA does not disrupt the hydrogen bond network established between ChCl and the HBD. Among the strongest interactions are those hydrogen bonds between the quinic acid moiety and the ethylene glycol or the urea. In addition, the thermochemistry of the formation of the two main deep eutectic solvents and their corresponding complexes with CGA was calculated, where the formation of urea-based structures was slightly more effective by ~3 kcal/mol.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50153064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of Cucurbit[7]uril on contrasting binding with flavonoids: Insights from spectroscopy and calorimetric studies 葫芦[7]uril与黄酮类化合物的对比结合作用：光谱学和量热法研究的启示

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-07-13 DOI: 10.1002/poc.4559

Rabindranath Jana, Souvik Pandit, Sanyukta Bhattacharjee, Debabrata Seth

引用次数: 0

DFT investigations on the mechanisms and kinetics for the DMS + O3 reaction DFT研究了DMS + O3反应的机理和动力学

IF 1.8 4区化学

Journal of Physical Organic Chemistry Pub Date : 2023-07-07 DOI: 10.1002/poc.4558

Shuangjun Wang, Hui Zhao, Dong Chen, Chenggang Lu, Yizhen Tang

{"title":"DFT investigations on the mechanisms and kinetics for the DMS + O3 reaction","authors":"Shuangjun Wang, Hui Zhao, Dong Chen, Chenggang Lu, Yizhen Tang","doi":"10.1002/poc.4558","DOIUrl":"10.1002/poc.4558","url":null,"abstract":"The potential energy surface (PES) for the reaction of ozone with dimethyl sulfide (DMS) was calculated at the CCSD(T)/6-311++G(3df,2pd)//M06-2X/6-311++G(d,p) levels of theory. Result shows that on the singlet PES the addition–elimination mechanism is dominant, and H-abstraction mechanism is less competitive. The major channel starts from the addition of ozone and DMS leading to a weak intermediate IM1, which decomposes subsequently to DMSO and 1O2 via a barrier around 38.8 kJ/mol. With a barrier of 64.0 kJ/mol, the formation of HO3 + CH3SCH2 via H-abstraction mechanism is subdominant. Besides, DMSO + 1O2 can take place further reactions to produce several products. The substitution mechanism was located on the triplet PES, however, with a rather high barrier it is negligible. Furthermore, the rate constants for the two channels leading to DMSO + 1O2 and HO3 + CH3SCH2 were calculated from 200 to 1000 K. The total rate constant is 1.13 × 10-20 cm3·molecule-1·s-1 at 298 K and 1 atm, in good agreement with previous experimental data. The overall rate constants are positive temperature dependent in the whole temperature range.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47914266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0